Stabilized system containing metal hydroxyalkyl phosphonic acid or phosphinic acid

ABSTRACT

ORGANIC MATERIALS NORMALLY SUBJECT TO OXIDATIVE DETERIORATION ARE STABILIZED BY INCORPORATING THEREIN A METAL DERIVATIVE OF MONOBASIC OR DIBASIC HINDERED PHENOL SUBSTITUTED PHOSPHONIC ACID AND ONE OR MORE OF THE ADDITIONAL ADDITIVES SELECTED FROM THE PHENOLIC ANTIOXIDANTS, SYNERGISTS, ULTRAVIOLET LIGHT ABSORBERS, ULTRAVOILT LIGHT STABILIZERS, BUFFERS, PIGMENTS, OR DELUSTERING AGENTS, DYES, DYESITES AND PHOSPHITES.

sa s Pateiflt'p 1 3,824,192 STABILIZED SYSTEM CONTAINING METAL HYDROXYALKYL PHOSPHONIC ACID R PHOSPHINIC ACID j Anthony Dominic DiBattista, 19 Douglas Place, Eastchester, N .Y. 10707, and John Denon'Spivack, 1 Blue Jay St.',--Spring Valley, NY. 10977 a No Drawing. Continuation of abandoned application Ser. Norv$54,281, .Aug. 29, 1969. This application Dec. 21, 1971, Ser. No. 210,584

.Int. Cl. C08 k 1/58, 1/60 U.s. Cl. 252-400 A 15 Claims 7 ABSTRACT OF THE DISCLOSURE Organic materials normally subject to oxidative deterioration are stabilized by incorporating therein a metal derivative of monobasic or dibasic hindered phenol substituted phosphonic acid and one or more of the additional additives selected from phenolic antioxidants, synergists, ultraviolet light absorbers, ultraviolet light stabilizers, buffers, pigments, or delustering agents, dyes, dyesites and phosphites.

This is a continuation of application Ser. No. 854,281 filed on Aug. 29, 1969, and now abandoned.

DETAILED DESCRIPTION wherein M is a metal having an available valence of from 1 to 4;

G is an anion having an available valence of from 1 to 3;

and 1 v l r E is of the formula;

Q (lower) alkyl H0 j a -(0,H,,)

wherein 1 2 has a value of from 0 to 6,

y has a value of froml to 4,

n has a value of from '0 to 1,

m has a value of from 1 to 3,

x has a value of from 1 to 2, and p has a value of from 0 to 3,

n, m, p and at being so selected as to satisfy the expression wherein r is the valence of anion G and has avalue of from 1 to 3 and v is the available valence of M. A

The group M consist either of a metal in full free valence state such as sodium, cadmium, zinc, barium, nickel, aluminum, tin, chromium, cobalt, iron, copper, titanium, vanadium, and the like, or of a metal derivative in which part but not all of its full free valence state is satisfied by 3,824,192 eted-Jab 1.974

ice

alkyl substitution, e.g. dialkyltin. Preferably M is a metal in its full free valence state, particularly those having a valence of 2 to 4 such as cadmium, zinc, barium, nickel, iron, copper, aluminum, tin, chromium,'titanium, vanadium, and cobalt. Of these, aluminum and the transitional metals, particularly nickel, are especially useful. The available valence bonds of the metal will be satisfied by one or more phosphonate or O-alkyl phosphonate groups and, if needed, by anions, organic or inorganic. Thus when n=0, there may be one (m-l) or more (n; =2 or 3) phosphonate groups. Likewise there may be one or more O-alkyl phosphonate groups (n=1). In some instances, as in the case of aluminum or chromium, three phosphonate groups combined with two metal atoms (x =2) to satisfy the valence requirements. In the case of mixed salts, one, two or three monovalent anions will make up the valence requirements. In all instances, the compounds will contain at least one phosphonate group or at least one O-alkyl phosphonate group and the values of n, m, p and x is such that the following expression is satisfied:

wherein r is the valence of anion G and has a value of from 1 to 3 and v is the available valence of M. r

The anion G may be organic or inorganic. Illustrative of such organic anions are carboxylate, such as those derived from carboxylic acids containing from 1 to 30 carbon atoms, preferably 2 to 18 carbon atoms, e.g. acetate, laurate, stearate, benzoate, malonate, maleate, succinate, and the like; phenates and alkyl substituted phenates; alkyland aryl-sulfates and -sulfonates; alkyland arylphosphates and -phosphon-ates; and inorganic anions such as chloride, bromide, fluoride, nitrate, cyanide, cyanate, sulfate, and the like.

As the embodiments of this invention, mention is made of compounds of the formulae:

(lower) alkyl wherein M, Z, y, n, m and 2: have the values defined above;

ower alk l y o (lower) alkyl wherein M, y, n, m and x have the values defined above; and most preferably CH C l a): O

(lower) alkyl wherein By the term al'kyl when used in this specification the appended claims, is intended a branched or straightchained saturated hydrocarbon group having from .1 to about 30 carbon atoms. When qualified by the term about 6 carbon atoms. Typical of such alkyl groups are' thus methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, isopentyl, hexyl, octyl, t-octyl, decyl, tetradecyl, hex-adecyl, octadecyl, eicosyl, docosyl, triacontyl and the like.

The phenyl group of phosphonate moiety is substituted by a hydroxy group and one (z=) or two (z=l to 6) (lower) alkyl groups. These substitutents may be located on the phenyl group in a number of ways. From the standpoint of maximizing the antioxidant properties, it is generally desirable to utilize a 3,5-dialkyl-4-hydroxyphenyl arrangement, e.g., 3,5-di-t-butyl-4-hydroxybenzylphosphonate. However, other arrangements such as 2- hydroxy--'(lower)alkylphenyl are also within the scope of the present invention.

The following formulae, in which K represents the group:

(lower)alkyl are typical structures of the compounds of this invention without being a limitation thereof:

The metal phosphonates of the present invention are prepared by treating a phosphonic acid or half-ester of the formula:

(lower) alkyl 2; CH )POH (VIII) wherein Z is hydrogen or alkyl, with the appropriate metal halide, such as the metal chloride. Preferably an alkali metal salt of VIII, such as the sodium or potassium salt, is employed. Generally the product is formed spontaneously or after a short reaction period and'need only be freed of by-products, solvents, and unreacted starting material, if any, as by Washing and extraction.

Illustrative examples of the metal phosphonates are:

nickel bis(O-octadecyl 3-rnethyl-4-hydroxy-5 t-butylbenzylphosphonate) I nickel bis(O-octadecyl 2-hydroxy-3,S-di-t-butylbenzyl V phosphonate) cupric bis[O-hexadecyl-(3,S-di-t-butyl-4-hydroxyphenyl)propylphosphonate] aluminum tris(O-butyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate) 1 7 ferric tris[O-0ctadecyl a-(3,5-di-t-butyl-4-hydroxyphenyl)ethylphosphonate] I chromium tris(O-butyl 3,5-di-t-butyl-4-hydroxybenzylav phosphonate) cobalt bis(O-butyl 3,5-di-t-butyl-4-hydroxybenzylphos-v phonate) stannous bis(O-butyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate) cadmium bis(O-butyl 3,S-di-t-butyl-4-hydroxybenzylphosphonate) barium bis(O-btuyl 3,S-di-t-butyl-4-hydroxybenzylphosphonate) zinc bis(O-butyl 3,5-di-t-butyl-4-hydroxybenzyl phosphonate) g dibutyltin bis (O-butyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate) barium 3,S-di-t-butyl-4-hydroxybenzylphosphonate dialuminum tris(3,S-di-t-butyl-4-hydroxybenzylphos-. phonate) cadmium 3,S-di-t-butyl-4-hydroxybenzylphosphonate nickel 3,5-di-t-butyl-4-hydroxybenzylphosphonate zinc 3,5-di-t-butyl-4-hydroxybenzylphosphonate nickel bis(O-octadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate) dibutyltin (3,S-di-t-butyl-4-hydroxybenzylphosphonate) nickel (O-n-butyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate)-chloride nickel (3,5-di-t-butyl-4-hydroxybenzylphosphonate)- acetate di-nickel-bis-(O-n-butyl 3,5-di-t-butyl-4-hydroxyben zylphosphonate sulfate nickel bis(O-ethyl 3,5-dimethyl-4-hydroxybenzylnickel bis(O-decyl 5-t-butyl-4-hydroxybenzylphosphonate) The metal derivativesof alkylhydroxyphenylalkylphosphinic acids that can be employed in the composition of this invention in place of the above discussed metal phosphonates are represented by the following formula: 7

wherein M is a metal or metal complex cation, this cation having an available valence of from 1 to 4;

g has a value of from 0 to 6;

g has a value of from 1 to 4; and

g has a value of from I, to 4, the value of 2 same as the available valence of M.

being the The group M consist either of a metal cation in a-free valence state such as the cation form of lithium, sodium, potassium, copper, magnesium, calcium, zinc, strontium; cadmium, barium, aluminum, titanium, zirconium, tin,

vanadium, autim9l l',,chromium, vmoly bdenum, manganese, iron, cobalt and the like. Alternatively the group M may be a metal complex iri which part but not all of the free vale'nces'tate of the metal is" satisfied by one or moreorganic or inorganic 'anions. Illustrative'of such organic anions are the acyloxy group derived froin'carboxylic acids containing from 11030 carbon atoms, preferably 2 to 18 carbon atoms, e.g., acetoxy, lauroyloxy, stearoyloxy, benzoyloxy,"malonoyloxy, succinoyloxy, and the like; phenoxy including alkylphenoxy; alkyl; alkyland arylsulfates and -sulfonat es; alkyland arylphosphates and -phosphonates and the like. Suitable inorganic anions include chloridesfbr'omides, fluoride, nitrate, cyanide, cyanate'fsulfate and the like. Of these metal complexes,'particularly useful species are represented by dialky'ltin'and nickel monoa'ceta'te.

The phenylalkyl group of phosphinic acid moiety is substituted in thear'omatic' ring by a hydroxy group and one (=0) or two 1 to 6), (lower) alkyl groups. These substituents may be located on the phenylalkyl group in a number of --ways.;From .the standpoint of maximizing the antioxidant properties, it is generally desirable to utilize a 3,5;dialkyl 4 hydroxyphenylalkyl arrangement, e.g., 3,S-di-t-butyl-4 hydroxybenzylphosphinate. However, other arrangements such as Z-hydroxy-S-(lower)alkylphenylalkyl are also within the scope of the present invention. 3-}

Although the struct ral formula on page 3 is presented in relation to the principal primary v-alences exhibited by the metal M, it is well known that many metals, especially the transition metals also commonly exhibit secondary valence forces which can bind the metal to other species in the immediate environment in which these compounds are made or used.

This is especially apparent when such valences are electronegativein character. Such'species may include moistureforming hydrates, alcohols, binding alcohol of crystallization, hydrocarbons, solvents especially aromatics, esters, ketones, etc; These metalphosphonate compounds may even bind with themsel-ves, yielding aggregates in relativ'ely non-polar." medium rather than exist by themselves in monomeric forms. Thus if M is Ni, as many as four additional secondary valence bonds may be involved in coordinating other molecules in the environment as described'above.

The "alkylhydroxyphenyl group is linked to the phosphinic acid group through 'a straight or branched chained alkylene group of from 1 to 4 carbon atoms, the number of carbon atoms ebing shown by the designation y.

' Tn addition to the alkylhydroxyphenyl-alkyl group, the phosphorus atom of the phosphinic acid group bears a hydrocarbon group of fromone to twelve carbon atoms. This hydrocarbon group may be an aliphatic hydrocarbon group, notably alkyl and'preferably (lower) alkyl, a cycloaliphatic hydrocarbon group, such as cyclopentyl, or cyclohexyl, or an aromatic hydrocarbon group such as phenyl, naphthyl, xylyl, and the like.

A particularly useful subclass of the present invention are thosecompounds of the formula:

(lower alkyl) "6 Il1ustrativ e examples of the metal derivatives of phosphinic acids described above are:

sodium (3,S-di t-butyl-4-hydroxybenzyl)benzenephosphinate' 1 barium bis- [-('3,5-di-t-butyl 4-hydroxybenzyl)benzenephosphinate 1 nickel bis- (3,S-di-t-butyl-4-hydroxybenzyl)- benzenephosphinate] aluminum tris-['63,S-di-tbutyl- 4-hydroxybenzyl)- benzenephosphinate] tin bis-[ ('3,S-di-t-butyl-4-hydroxybenzyl)benzenephosphinate] dibutyltin bis-[-( 3,S-di-t-butyl-4-hydroxybenzyl)- Y benzenephosphinate] nic'kel [l(3,S-di-t-butyl-4-hydroxybenzyl)benzenephosphinate1acetate calcium bis- 3,5 -di-tbutyl-4-hydroxybenzyl)- benzenephosphinate] zinc bis- 3 ,5-di-t-butyl-4-hydroxybenzyl) -benzenephosphinate] sodium ["2 (3,S-dit-butyl-4-hydroxyphenyl)ethyl]- benzenephosphinate nickel bis- [2-( 3 ,5 -di-'t-butyl-4-hydroxyphenyl) ethyl] benzenephosphinate sodium [2(3,5-di-t-butyl-4-hydroxyphenyl)ethyl}- ethanephosphinate aluminum tris[2-(3,5-di-t-butyl-4-hydroxyphenyl)- ethyl]ethanephosphinate sodium (3 5-di-t-butyl-4-hydroxybenzyl)cyclohexane phosphinate nickel bis-['(3,S-di-t-butyl-4-hydroxybenzyl)cyclohexanephosphinate] nickel bis 3,5 -di-isopropyl-4-hydroxybenzyl) benzenephosphinate] nickel bis[3-methyl-4-hydroxybenzyl)benzenephosphinate] nickel bis [3, 6-dimethyl-4-hydroxyvbenzyl)benzenephosphinate] nickel bis ['3,5-diethyl-4-hydroxybenzyl) benzenephosphinate] nickel bis[3,6-di-n-hexyl-4-hydroxybenzyl)benzenephosphinate] The preparation of the above discussed metal derivatives of phosphinic acids is described in copending application Ser. No. 612,336, filed Jan. 30, 1967, now Pat. No. 3,488,368.

The antioxidants that are advantageously employed with the above mentioned phosphonic acids and esters are generally phenolic antioxidant compounds. Examples of the phenolic compounds are given below.

(1) Phenolic compounds having the general formula wherein Qis -R is hydrogen or lower alkyl R is lower alkyl IR" is alkyl group having from 6-24 carbon atoms w is an integer from 1 to 4. i I? Illustrative examples of the compounds shown above are 110- 0 CHrC COOCiaHw di-n-octadecyl(3-t-butyl-4-hydroxy-5-methylbenzyl) malonate di-n-octadecyl @(3 t butyl-4-hydroxy-S-methylbenzyl) malonate which is disclosed in the Netherlands Patent No. 6711199, February 19, 1968 di-n-octadecyl u,ot' bis-(3-t-butyl-4-hydroxy-5-methylbenzyl)malonate which is disclosed in the Netherlands Patent No. 6803498, September 18, 1968. (2) Phenolic compounds having the general formula Illustrative examples of the compounds shown above are 2,6-di-t-butylphenyl 2,4,6-tri-t-butylphenol 2,6-dimethylphenol 2-methyl-4,6-di-t-butylphenol and the like.

(3) Phenolic compounds having the formula 2,2-methylene-bis 6-t-butyl-4-methylphenol) 2,2-methy1ene-bis(6-t-butyl-4-ethylphenol) 4,4'-butylidene-bis (2,6-di-t-butylphenol) 4,4'-(2-butylidene -bis (2-t-butyl-5-methylphenol) 2,2'-methy1ene-bis 6-( l-methylcyclohexyl -4-methylphenol and the like.

(4) Phenolic compounds having the formula Illustrative examples of such compounds are 2,S-di-t-butylhydroquinone 2,6-di-t-butylhydroquinone 2,6-di-t-butyl-4-hydroxyanisole (5) Phenolic compounds having the formula Illustrative examples of such compounds are 4,4-thiobis-(2-t-butyl-5-methylphenol) 4,4'-thiobis-(2-t-butyl-6-methylphenol) 2,2'-thiobis-(6-t-butyl-4-methylphenol) (6) Phenolic compounds having the formula Illustrative examples of such compounds are octadecyl-(3,5-dimethyl-4-hydroxybenzylthio)-acetate dodecyl-(3,5-di-t-butyl-4-hydroxybenzylthio)-propionate (7) Phenolic compounds having the formula wherein T is hydrogen, R or Q as defined above.

8 -'-Il lustrative examplesof such compounds are 1,1,3-tris 3,S-dimethyl-4-hydroxyphenyl propane f 1,1,3-tris(5 t butylA hydroxy 2-methylphenyl)-butane 1,1,5,5-tetrakis-( 3'-t-butyl-4f-liydroxy6'-methylphenyl) n-pentane v y y (8) Phenolic compounds having the formula I v on: drun wherein B B and B are hydrogen, methyl or Q, provided that when B and B are Q then B is hydrogen or methyl and when B is Q then B and B are hydrogen or methyl. 7.

Illustrative examples of such compounds are 1,4-di(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-

tetramethylbenzene u l,3,5-tri(3,S-di-t-butyl-4-hydroxybenzyl)-2,4,6-

trimethylbenzene (9) Phenolic compounds having the formula ZiS NHQ,SD or Q D is alkyl group having from 6-12 carbon atoms or C H )4-R" v v Illustrative examples of such compounds are I 2,4-bis-(n-octylthio)-6-( 3,5 -di-t-butyl-4-hydroxyaniline)- 1,3,5-triazine 6-(4-hydroxy-3-methyl-5-t-butylanilino-2,4-bis-(noctylthio)-1,3,5-triazine 6-(hydroxy-3,S-dimethylanilino)-2,4-bis1(n-octylthioy 1,3,5-triazine 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis-(n-octylthioethylthio)-l,3,5-triazine I 6-(4-hydroxy-3,5-di-t-butylanilino)-4-(4-hydroxy-3,5-

di-t-butylphenoxy)-2-(n-octylthio)-1,3,5-triazine 2,4-bis(4-hydroxy-3,5-di-t-butylanilino)-6-(n-octylthio);

1,3,5-triazine. v I

The above phenolic triazine stabilizers are more fully described in US. 3,255,191.

(10) Phenolic compounds having theformula' wherein Z is -O-Q, SD or -'-S-(C,H )SD Illustrative examples of such compounds are 1 1 2(2'-hydroxy-5'-methylphenyl)benzotriazole 2(2-hydroxy-3,5-di-t-butylphenyl)-7-chlorobenzotriazole 3 Nickel acetylacetonate Dipropylene glycol salicylate Phenyl salicylate Sucrose benzoate Lauroyl-p-aminophenol 2-(2-hydroxy-3,S-di-t-amylphenyl)benzotriazole Nickel-bis 2,2'-thiobis- 4-t-octylphenol) Nickel-bis(butyldithiocarbonate) 2-Hydroxy- 4-(2-hydroxy-3-methacrylyloxy)- propoxybenzophenone 2-Hydroxy-4- (2hydroxy-3-acrylyloxy) -prop oxybenzophenone.

In addition to the above mentioned additives the present invention also covers the use of secondary antioxidants. When such secondary antioxidants are employed in combination with the primary antioxidants the stabilization achieved is greater than the additive effect of the two antioxidants. Illustrative examples of such secondary antioxidants are distearylthiodipropionate, dilaurylthiodipropionate, trisnonylphenylphosphite, trilauryl-trithiophosphite and the like.

Often in order to achieve optimum stabilization it is necessary to employ buffers or corrosion inhibitors. Such additives can be conveniently employed in combination with other additives disclosed herein. Illustrative examples of buffers or corrosion inhibitors are calcium stearate, calcium oxide, magnesium stearate, epoxides and the like.

Dyesites can also be employed in combination with the various additives discussed herein. Illustrative examples of dyesites are poly(2-vinylpyridine), polyvinylpyrrolidone, polyvinylalcohol, 2,2-thio-bis(4-t-octylphenol)nbutylamine nickel (II) nickel stearate, alumino-silicate composed of silicon dioxide and aluminum oxide, fiuoro alcohols such as 2,2,3,3 tetrafluorocyclobutyl methanol, 2,5 di (2,hydroxyphenyl)-thiazole[5,4-d-]thiazole, octadecyllepichlorohydrin/piperazine (0.3/ 1.3/1 polycondensate), dichloroethane/hexamethylene diamine condensate/alkylated with lauryl chloride (1/ l/0.12), bis- (Z-mercaptoethyl) piperazine, piperazine, N-aminoethylpiperazine, 3 methyl 5 amino-thiadiazole 1,2,4,2- amino 4,5 dimethyl-thiazole 1,3,2 amino-triazole- 1,3,4-poly(pheny1ene methyltriazole), poly(tetramethylene-N-benzal-aminotriazole), poly(phenylene acetaminotriazole), poly(2,4-di-methyl-6-vinyl pyridine), 75/25 copolymer 2-methyl-5-vinyl pyridine/N, n-dimethylacrylamide, 70/10/20 copolymer N-isopropylacrylamide/N,N- dimethylacrylamide/2-methyl-5-vinyl pyridine and the like. The dyesite can be added to a polymer to be dyed in an amount up to about by Weight of the polymer.

Polymers stabilized by incorporating therein various additives of this invention may also be dyed with various organic dyes or inorganic pigments. Illustrative examples of dyes and pigments are:

Kiton Fast Blue G-Acid Blue 43C.I. 63000 Hadacid Blue A Conc.--Acid Blue 7C.I. 42080 Polar Red 3BAcid Red 134--C.I. 248 10 Lexanol Yellow 6G-Acid Yellow 44--C.I. 23900 Wood Red BAcid Red ll5-'-C.I. 27200 Alizarine Yellow 2GYellow 1C.I. 14025 Alizarine Red S-Wordant Red 3C.I. 58005 Acid Black JVSAcid Black 1C.I. 20470 Setacyl brilliant blue E.G.disperse blue 3C.I. 61505 Blue, monochloro-4,S-diaminochrysazin Blue, l,4-diamino-N-(3-methoxypropyl)-2,3-anthraquinonedicarboximide (US. Pat. 2,753,356)

Blue, 1,4-diamino-N-(S-hydroxypropyl)-2,3-anthraquinonedicarboximide (US. Pat. 2,628,963)

Blue, 1,4-diarnino-N-(2-hydroxyethyl)-2,3-anthraquinonedicarboximide (US. Pat. 2,628,963) 7 Violet, 1,4-dianilinoanthraquinone Violet, 1-anilino-4-hydroxyanthraquinone 12' Yellow, 3-hydroxyquinophthalone Red, 1-amino-4-hydroxy-2-phenoxyanthraquinone Orange, disazo dye obtained by coupling diazotized aniline to 2,5-dimethoxyaniline, disazotizing the amino azo dye formed and coupling to phenol Bone blackBlack 9-C.I. 77267 Carbon blackBlack 7C.I. 77266 Indanthrone-Blue 22-C.I. 69810 Phthalo GreenGreen 7C.I. 74260 Phthalo BlueBlue 15C.I. 74160 Thioindigoid-Vat Violet 2 and 3C.I. 72385 and 73395 Bon Maroon- Red 58C.I. 15825 Red 48- C.I. 15865 Red 63C.I. 15880 C.I. Solvent Black 29 C.I. Solvent Red 133 C.I. Solvent Blue 48 C.I. Solvent Green 21 C.I. Solvent Brown 42, 43 and 44 C.I. Solvent Black 30 C.I. Solvent Orange 57, 58 and 59 C.I. Solvent Red 129 to 132 and 134 C.I. Solvent Yellow 88 to 91 Pigment Orange 42 Pigment Red 180 Pigment Violet 34 and 35 Pigment Yellow 109 and 110 Titanium dioxide Iron oxide Chromium oxide Chrome-cobalt-alumina Cobalt aluminate Zinc chromate Manganese Chrome-tin Cadmium-mercury Cadmium sulfo-selenide Zinc oxide Zinc sulfide and the like.

Still another type of additive that may be employed is a co-light stabilizer which may be hindered hydroxybenzoic acid esters such as 2,4-di-t-butylphenyl-3,S-di-t-butyl-4-hydroxybenzoate methyl 3-methyl-5-isopropyl-4-hydroxybenzoate ethyl 3,5-diisopropyl-4-hydroxybenzoate propyl 3,5-di-sec-butyl-4-hydroxybenzoate isobutyl 3,5-di-tert-amyl-4-hydroxybenzoate amyl 3,S-di-tert-heptyl-hydroxybenzoate decyl 3,5-di-tert-octyl-4-hydroxybenzoate cyclohexyl 3,5-di-tert-amyl-4-hydroxybenzoate lauryl 3-methyl-S-isoamyl-4-hydroxybenzoate stearyl 3,5-diisopropyl-4-hydroxybenzoate palmityl 3,5-di-tert-butyl-4-hydroxybenzoate chloromethyl 3,5-di-tert-butyl-4-hydr0xybenzoate 3-fiuoropropyl 3,5-di-tert-amyl-4-hydroxybenzoate allyl 3,5-di-tert-butyl-4-hydroxybenzoate 2-butenyl 3,5-diisopropyl-4-hydroxybenzoate oleyl 5-methyl-5-tert-amyl-4-hydroxybenzoate 3-cyclohexenyl 3,5-di-sec-heptyl-4-hydroxybenz0ate ethane-1,2 di(3,5-diisopropyl-4-hydroxybenzoate) propane-1,3 di(3,S-di-tert-amyl-4-hydroxybenzoate) pentane-1,5 di(3,5-di-tert-octyl-4-hydroxybenzoate) hexane-1,5 di(3-methyl-5-tert-butyl-4-hydroxybenzoate) 2-chloropropane-1,3 di(3,5-di-tert-butyl-4-hydroxybenzoate) phenyl 3,S-diisopropyl-4-hydroxybenzoates p-octylphenyl 3,S-di-terbamyl-4-hydroxybenzoate 2,4'-dimethylphenyl 3,5-di-tert-octyl-4-hydroxybenzoate p-isopropylphenyl 3-methyl-5-tert-amyl-4-hydroxybenzoate naphthyl 3,S-di-tert-butyl-4-hydroxybenzoate 6-methylnaphthyl 3,5-di-tert-hexyl-4-hydroxybenzoate 13 benzene-l,3,5-tri(3,5-diisopropyl-4 hydroxybenzoate benzene-1,2-di(3,S-di-tert-amyl-4-hydroxybenzoate p 'chlorophenylE3,Sdi-trt-butyl-4rhydroxybenzoate 2,4-dibromophenyl 3,5-diisopropyl-4-hydroxybenzoate -*rganic phosphites*can be employed in. the instant invention as secondary antioxidants. The useful phosphites are trialkyl and triaryl phosphites or amixture thereof and a1ky1 or aryl hydrogen phosphites, such as dialkyl hydrogen phosphites, diaryl hydrogen phosphites and'alkyl aryl hydrogen phosphites. Illustrative examples are tridodecylphosphite trioctadecylphosphite, trinonylphenylph nhit of I. T

Still other additives that can be incorporated into the compositions of this invention are'metal deactivators such as oxamide, oxani lide, N,N'-disalicylalaxaldihydrazide and N -salicylidene-N' salicylhydrozine.

As already noted earlier, the instant invention envisions the use of any 'one or more of the above additives, in any combination; together with the metal phosphonates and phosphinates'described above. By employing such a combination olf additivesin polymers, and especially in polyolefins, the resulting' mroducts attain an unusual degree of stabilization against degradation caused by oxygen, heat, ultraviolet light and the like. The supplementaryadditives, that is, antioxidants, secondary antioxidants, 'ultra tv iol'e'at light absorbers, light absorbers, buffers or corrosion inhibitors, pigments or dyes and dyesites are generally used in the amount of from about 0.001 to about by weight of each additive. The preferred r n is from about 0.01 to about 1% by weight of the substrate (up to 3 for polymeric dyesites).

The stabilization system of the present invention is useful of stabilizing of organic materials normally subject to oxidative'orthermal deterioration. Materials which are thus stabilized include synthetic organic polymeric substances" sl'ich'as" vinyl resins formed from the polymerization of vinylhalides or from the copolymerization of vinyl halides with unsaturated polymerizable compounds, e.g., vinyl esters, a,B-unsaturated aldehydes and unsaturated hydrocarbons such as butadienes and styrene, polyni-olefins suchuas vpolyethylene, polypropylene, polybutylene,-polyisoprene,,and the like, including copolymers of poly-aolefins, polyurethanes such as are prepared from polyols and organic ifpolyisocyanates; polyamides such as polyhexamethylene adipamide and polycaprolactam, polyesters such as polymethylene or polyethylene terephthalates;polycarbonates; polyacetals; polystyrene; polyethyleneoxide'; and copolymers" such as those of high impact polystyrene containing copolymers of butadiene and styrene and those formed'by the copolymerization of "acrylonitrile, butadiene and/or styrene. Other materials' stabilized according to the present invention include lubrication oil of the aliphatic. ester type, e.g., (di)2- ethylhexyl)-azelate, pentaerythritol tetracaproate and the like; animal and vegetable derived oils, e.g., linseed oil, fat, ,tallow, lard, peanut oil, cod liver oil, castor oil, palm'bil," corn oil, co'tton seed oil, and the like; hydrocarbon .materialsuchas gasoline, mineral oil, fuel oil, drying oil, cutting fiuides, waxes, resins, .and the like, fattyacida'soaps and thelike. I

Deterioration f most polymers caused by oxygen, heat 'or ultraviolet light is so slow at ambient temperatures, even in the absence oi stabilizers, that testing .of the effects of stabilizers generally must be conducted either at higher temperatures or in an accelerated artificial light exposure device in orderto yield'results in a convenient period of time. The tests conducted on polymers are describedbelowz Eu -"5 a 4:, H r-LIGHT STABILIZATION TESTS H vUt 5 1 11 P e a 25 mil plaquesI-Unstabilized polypropylene powder (Hercules Profax 6501) is thoroughly blended with the indicated-amounts of additives. The blended materialis 14 then milled on a two roll mill for 5 minutes at 182. The milled sheet is then compression molded at 220 C. into 25 mil thick plaquesu'nder a pressure of psi. and water cooled in the press.

3 mil oriented monofilaments.A portion of the milled sheet prepared above ischarged into an Extrusion Plastometerand melt spun at 250 C. into a monofilament through the orifice normally used for obtaining a melt index. The filament is air cooled, wound on a set of hot Godet rolls and oriented 4:1 by a second set of cold Godet rolls. The monofilament is finally wound on a spoo a (b) Testing methods 25 mil plaques.-This test is conducted in a FS/BL unit, basically of the American Cyanamid design, which consists of 40 tubes of alternating fluorescent sun lamps and black lights (20 of each).) The 25 mil sample plaques which are mounted on white cardboard stock are placed on a rotating drum 2 inches from the bulbs. The plaques are exposed in the -FS/BL unit until they become sufiiciently brittle to break cleanly when bent 180. The results are recorded as hours of exposure to embrittlement.

3 mil monofilaments.The oriented monofilament is wound ten times around a 2 inch wide strip of white cardboard stock under slight tension and exposed in the FS/ BL unit described above. At intervals of approximately 2 days the filaments are tested for brittlenes by the appllcatlon of slight finger pressure across the strands. The results are recorded as hours of exposure until the time when the strands break easily.

Test results reported in Examples 1 to 15 were obtained according to the procedures described above. The amounts of the additives are expressed in weight percent based on the weight of the polymer.

Unstabilized polypropylene samples prepared by the above described procedures yield the following results:

Hours 3 mil monofilament 150 25 mil plaques 50 EXAMPLE 1 Polypropylene was blend with the folowing additives:

0.5 2 (2'-Hydroxy-3 ',5'-di-t-butylphenyl) -7-chlorobenzotriazole 0.5 Nickel bis (O-n-butyl-3,5di-t-butyl-4-hydroxybenzyl) phosphonate] Hours 3 mil monofilament 700 1425 25 mil plaques EXAMPLE 2 Polypropylene was blended with the following additives:

0.5% 2(2-Hydroxy-3',5'-di t-butylphenyl)-7-chlorobenzotriazole 0.5% O-n-Butyl-chloronickel-3,5-di-t-butyl-4-hydroxybenzyl phosphonate Hours 3 mil monofilament 550 25 mil plaques 1500 Improved results are obtained when in Examples 1 and} are additionally employed.

EXAMPLE 3 Polypropylene Was blended with the following additives:

0.5% 2-Hydroxy-4-n-octoxybenzophenone 0.5% Nickel bis[(O-n-butyl-3,5-di-t-butyl-4-hydroxybenzyl)phsphonate] Hours 3 mil monofilament 1000 25 mill plaques 1425 EXAMPLE 4 Polypropylene was blended with the following additives:

0.5% 2-Hydroxy-4-n-octoxybenzophenone 0.5% O-n-butyl-chloronickel-3,5-di-t butyl-4-hydroxybenzyl phosphonate Hours 3 mil monofilament 550 25 mil plaques 1400 Similar results are obtained when in Examples 3 and 4 the nickel phosphonates are replaced with Nickel-bis-(3,5-di-t-butyl-4-hydroxybenzyl)benzenephosphinate Nickel-bis-[ O-methyl-3,5-di-t-butyl-4-hydroxybenzyl) phosphonate] EXAMPLE 5 Polypropylene is blended with the following additives: 0.25% Dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate 0.75 Nickel bis[(O-n-butyl-3,5-di-t-butyl-4-hydroxybenzyl)phosphonate] Hours 3 mil monofilament 350 25 mil plaques 900 EXAMPLE 6 Polypropylene was blended with the following addi-, tives: 0.25% Octodecyl ,8-(3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.75% O-n-butyl-chloronickel-3,5-di-t-butyl-4-hydroxybenzyl phosphonate Hours 3 mil monofilament 250 25 mil plaques 900 Improved results are obtained when in Examples 5 and 6 are additionally added 0.3% dilaurylthiodipropionate 2.0% titanium dioxide pigment EXAMPLE 7 Polypropylene was blended with the following additlves:

0.10% Octadecyl fl-(3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.15% Distearylthiodipropionate 0.75% O-n-butyl-chloronickel-3,5-di-t-butyl-4-hydroxybenzyl phosphonate I Hours 3 mil monofilament 325 25 mil plaques i I 850 16 EXAMPLE 8 Polypropylene was blended with the following addi; tives: v 0.10% Octadecyl fi-(3,5-di-t-butyl-4-hydroxy phenyl)propionate l v. 0.15% Distearylthiodipropionate 0.75% Nickel bis[(O-n-butyl-3,5edi-t-buty1-4-hydroxy benzyl(phosphonate] x lv Hours 3 mil monofilament "400 25 mil plaques "950'- EXAMPLE 9 Polypropylene was blended with the following additives? 0.1% Nickel bis[3,S-di-t-butyl-4 hydroxybeniyl)benienephosphinate] i v 0.5% Distearylthiodipropionate .v

25 mil plaques h0l1l'S 1 3 EXAMPLE l0 v Polypropylene was blended with the following additives 0.5% Nickel bis[(O-n-butyl 3,5-di-t-butyl t liydroxyberiz yl)phosphonate] 0.5% 2(2'-Hydroxy-3',5-di-t-butylphenyl) 7- elilofc-f" benzotriazole i Hours 3 mil monofilament 700 25 mil plaques 1425'- EXAMPLE 1-1 I A Polypropylene was blended with the following additives 0.5% Nickel bisi(o-n-bui l-s,5-di-ebuiylg i li di i ben yl)phosphonate] y L 0.5 2-Hydroxy-4-n-oct xybenzophenone Hours EXAMPLE 12 1 5,

EXAMPLE -13 c Polypropylene was blended with the followingadditivesi 0.5% Nickel bis[(3,5-di-tebutyl-4 hydroxybenzyl)benzenephosphinate i 0.1% Dioctadecyl 3,5-di-t-butyl 4 3 hydroxybenzylphos- Phon'ate r e 17 EXAMPLE 14 I Polypropylene was blended with the following additives: 0.5% O-n-butyl-chloronickel 3,5 di-t-butyl-4-hydroxybenzyl 0.4% 2(2'-Hydroxy 3,5' di-t-butylphenyl)-7-chlorobenzotriazole 0.1% Octadecyl [3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate Hours 3 mil monofilarnent 600 25 mil plaques 1425 EXAMPLE is Polypropylene was blended with the following additives:

0.25% Nickel bis[3,S-di-t-butyl-4-hydroxybenzyl)benzenephosphinate 0.1% Dioctadecyl 3,5 di-t-butyl-4-hydroxybenzylphosphonate 0.25% 2(2-Hydroxy 3,5' dit-buty1phenyl)-7-chlorobenzotriazole Commercial nickel-containing polypropylene is stabilized with 0.2% Tin bis-(O-butyl 3,5di-t-butyl-4-hydroxy-benzylphosphonate I 0.05 Nickel 3,5-di-t-butyl-4-hydroxybenzyl )benzenephosphinate]acetate,

0.1% 2,4 Bis-(n-octylthio)-6-(3,5-di-t-butyl-4-hydroxyaniline)-1,3,5-triazine,

0.05% 2-Hydroxy-4-n-octoxybenzophenone,

0.02% dilaurylthiodipropionate.

3.0% Poly(2-vinylpyridine) and 0. 1% 2,4-Di-t-butylphenyl-3,S-di-t-butyl-4-hydroxybenzoate.

Said polypropylene composition is then dyed with the fol lowing dyes:

Kiton fast bluez; CI; 63000. 1

Polar red: CI. 24810 Lexanol yellow: CI. 23900 Acid black JVS: C.I. 20470 Phthalo green: CI. 74260 Bon maroon: C.I.15825 Equally good stabilization is obtained when in Exam: ple 18 2,4-bis-n(octylthio 6'- (3,5-di-t-butyl-4-hydroxyaniline)-1,3,5 triazine is replaced with 2,2'-methylenebis-6-t-butyl-4-methylphenol), 2,6-di-t-butylhydroquinone, 4,4" thiobis-(Z-t-butyl-S-methylphenol), octadecyl-(3,5- dimethyl 4 hydroxybenzylthio)acetate or 1,1,3-tris-(- t-butyl 4 hydroxy-2-methylphenyl)-butane.

18 EXAMPLE 19 Butadiene-styrene-acrylonitrile copolymer is stabilized with 2.0% Aluminum tris(O-butyl-3,5-di-t-butyl-4-hydroxybenzylpho sphonate) 0.1 2,4-Bis- (3 ,5 -di-t-butyl-4-hydroxyphenoxy) -6- (no-octylthio)-1,3,5-triazine,

0.1% 2-Hydroxy-4-methoxy-2'-carboxybenzophenone,

0.05% Distearylthiodipropionate and 0. 1 3,5-Diisopropyl-4-hydroxybenzoate.

Equally good stabilization is attained when in Example 19 the aluminum phosphonate is replaced with Sodium(O-butyl-3,5-di-t-butyl-4hydroxybenzylphosphonate) Cupric bis [O-hexadecyl-l 3,5 -di-t-buty1-4-hydroxyphenyl) propylphosphonate] Ferric tris [-O-octadecyl ;8(3,5-di-t-butyl-4-hydroxyphenyl)ethylphosphonate] Chromium tris (O-butyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate) Cobalt bis (O-butyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate.

EXAMPLE 20 Nylon pellets are blended with 0.5% Stannous bis(O-butyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate,

0.25 l,4-Di(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-

tetramethylbenzene and 0.25% 2,4-Dihydroxybenzophenone.

Substantially the same degree of stabilization is obtained when 2,4-dihydroxybenzophenone is replaced with 2-Hydroxy-4-n-octoxybenzophenone 2-Chloro-2-hydroybenzophenone 4-t-Butyl-phenylsalicylate Resorcinol monobenzoate Hexamethylphosphoric triamide Nickel bisoctyl phenyl sulfide Ethyl-2-cyano-3,3-diphenylacrylate 2(2'-hydroxy-5-methylphenyl)benzotriazole Lauryl-p-aminophenol.

EXAMPLE 21 Polyvinylchloride is blended with the following additives to provide a stable composition:

1.5% Zinc 3,S-di-t-butyl-4-hydroxybenzylphosphonate 0.75% Dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate 0.5% 2-Ethylhexyl-2-cyano-3,3-diphenyl acrylate.

Similarly good stabilization is obtained when in Example 21 polyvinyl chloride is replaced with polyurethane, polymethylene terephthalate and polyacetal.

OUTDOOR EXPOSURE TESTS (a) Sample preparation 15 denier oriented multifilaments: The additives are dissolved in distilled methylene chloride and blended with polypropylene (Hercules Profax 6501) in a Hobart mixer. A Buifer (such as calcium stearate) and a pigment (such as titanium dioxide) are added dry to the polymer blend. To facilitate moisture removal all blends are vacuum dried shortly before extrusion.

Samples are processed as follows:

1. Compound and pelletizing:

1" Extruder: L/D=20/1 at 40 r.p.n1. Melt temperature: 450 F.

2. Multifilament:

1" extruder: L/D=24/1 at 20 rpm. Spinnerette: 10 hole, 2 0 mil diameter/hole Melt temperature: 500 F.

(b) Test methods for weathering stability Mockdyed knitted multifilament was exposed 45 south direct in Florida. Exposures were begun November 1. Tensile measurements were performed at each exposure interval with Instron Model TM.

6.5 mil oriented monofilaments: The additives are solvent blended (e.g. methylene chloride) with powdered polypropylene (Hercules Profax 6501). The solvent is then removed at room temperature in a vacuum oven with a slight air bleed. The dry mixture is melt-extruded at 450 F. and pelletized. The pellets are reextruded through a monofilament, melt spun and hot oriented 4:1 by means of a set of cold and hot Godet rolls to give 6.5 mil diameter (nominal) monofilaments.

The test results reported in Examples 22 to 33 show the percentage of retention of the original tenacity by a fiber after having been exposed to the indicated number of kilolangleys (kly.). A langley is a measure of energy accumulated by the fiber. It is common that some fibers after initial exposure increase their orientation. For this reason in some examples the percent of retention is more than 100. This usually occurs at lower energy levels, such as at 25 kly.

EXAMPLE 22 Polypropylene filaments containing the following additives were prepared as described above:

0.50% Nickel bis[(O-n-butyl-3,5-di-t-butyl-4-hydroxybenzyl)phosphonate] 0.10% Dioctadecyl 3,S-di-t-butyl-4-hydroxybenzylphosphonate 0.25% Distearylthiodipropionate 0.10% Calcium stearate 2.00% Titanium dioxide Percent 25 kly. 107.0 50 kly. 53.0

EXAMPLE 23 Polypropylene filaments containing the following additives were prepared as described above:

0.10% Nickel-bis- ['2,2-thiobis( 4-t-octyl-phenolate) 0.10% Dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate 0.25 Distearylthiodipropionate 0.10% Calcium stearate 2.00% Titanium dioxide Percent 25 kly. 77.3 50 kly. 31.0

EXAMPLE 24 Polypropylene filaments containing the following additives were prepared as described. above:

0.50% Nickel bis[(O-n-butyl-3,5-di-t-butyl-4-hydroxybenzyl)phosphonate] 0.10% Dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate 0.25 Distearylthiodipropionate 0.50% 2-Hydroxy-4-n-octoxybenzophenone 0.10% Calcium stearate I 2.00% Titanium dioxide Percent 25 kly. 118.0 50 kly. 80.0

EXAMPLE -25 Polypropylen'e filaments containing'theffollowirig ad tives were prepared as described above: I 0.50% Nickel bis[(O-n-butyl-3,5dirt-butyl-4 hyd roxy-,.

I Percent 25 kly. 94.1

50 kly. f 68.7

EXAMPLE 26' Polypropylene filaments containing the following additives were prepared as described above: 1

0.5 0% Nickel bis[ (O-n-butyl-3,5-dirt-butyl-4-hydroxybenzyl)phosphonate] 0.10% Dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate 0.25% Distearylthiodipropionate" I I 0.50 2- 2'-hydroxy-3 ',5 -di-t-anylphenyl) 1 ,2,3,-benzotriazole z i 0.10% Calcium stearate I 2.00% Titanium dioxide I h I p p Percent 25 kly. 92.6 50 kly. 72.4

EXAMPLE 27 Polypropylene filaments containing thefollowing additives were prepared as described above:

0.10% Dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate I 0.25 Distearylthiodipropionate 0.5 0% 2 2-hydroxy-3 ',5 -di-t-butylphenyl -7-chlorobenzotriazole 0.10% Calcium stearate 2.00% Titanium dioxide 50 kly.: 31.3 (tenacity retained) The above formulation containing 0.2% dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate 5O kly.: 38.5% (tenacity retained) It should be noted that in this example the polypropylene formulation contained no organonickel compound of this invention.

EXAMPLE 28 Polypropylene filaments containing the following additives were prepared as described above:

0.10% Dioctadecyl 3,S-di-t-butyl-4-hydroxybenzylphosphonate 0.25% Distearylthiodipropionate 0.50% 2-Hydroxy-4-n-octoxybenzophenone 0.10% Calcium stearate 2.00% Titanium dioxide 50 kly.: 33.9% (tenacity retained) The above formulation containing 0.20% Dioctadecyl 3,S-di-t-butyl-4-hydroxybenzylphosphonate so kly.: 31.0% (tenacity retained) 21. EXAMPLE 29 Polypropylene filaments containing the following addi tives were prepared as described above:

0.20% Dioctadecyl 3,S-di t-butyl-4-hydroxybenzylphosphonate 0.25% Distearylthiodipropionate 0.10% Calcium stearate 2.00% Titanium dioxide 50 kly.: 28.2% (tenacity retained) It should be noted that in this example the polypropylene formulation contained neither the organonickel compound of this invention nor an ultraviolet light absorber.

EXAMPLE 30 Polypropylene filaments containing the following additives were prepared as described above:

1.0% Nickel bis-[ (3,5-di-t-butyl 4 hydroxybenzyl)benzenephosphinate] 0.1 Dioctadecyl 3,5-di-t-butyl 4 hydroxybenzylophosphonate 0.1% Calcium stearate 40 kyl.: 72% tensile strength retained, 88% elongation retained EXAMPLE 31 Polypropylene filaments containing the following additives were prepared as described above:

1.0% Nickel bis-[(3,5-di-t-butyl 4 hydroxybenzynbenzenephosphinate] 0.1% Dioctadecyl 3,5 di t butyl-4-hydroxybenzylphosphonate 0.1% Calcium stearate 0.5% 2(2'-hydroxy-3',5'-di-t-butylphenyl)-7-chlorobenzotriazole 40 kly.: 97% tensile strength retained, 93% elongation retained EXAMPLE 32 Polypropylene filaments containing the following additives were prepared as described above:

0.5 Nickel bis-[ (3,5-di-t-butyl 4 hydroxybenzyl)benzenephosphinate] 0.1% Dioctadecyl 3,5 di t butyl-4-hydroxybenzylphosphonate 0.1% Calcium stearate 40 kly.: 94% tensile strength retained, 90% elongation EXAMPLE 33 Polypropylene filaments prepared in the same way as in Examples 27 to 29, except without the stabilizing additives:

40 kly.: About 20% tensile strength retained, 20% elongation retained EXAMPLE 34 Polypropylene was blended with the following additives:

0. 1% Nickel bis (3 ,5-di-t-butyl-4-hydroxybenzyl) benzenephosphonate] 0.1% Dioctadecyl 3,5 di t butyl-4-hydroxybenzylphosphonate 0.1% Calcium stearate 6 mil monofilament: 40 kly., 72% tensile strength retained; 70 kly., 63% tensile strength retained; 90 kly., tensile strength retained Similar result is obtained when in this example dioctadecyl 3,5-di-t-butyl 4 hydroxybenzylphosphonate is replaced with Octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate Tetra [3-(3,S-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]-methane 6 mil monofilament: 40 kly., 97% tensile strength retained; 70 kly., tensile strength retained; 90 kly., 84% tensile strength retained.

EXAMPLE 36 Polypropylene was blended with the following additives:

0.5 Nickel bis[ (3,S-di-t-butyl-4-hydroxybenzyl) benzenephosphinate 0.1% Dioctadecyl 3,5 di t butyl-4-hydroxybenzylphosphonate 0.5% 2-Hydroxy-4-n-octoxybenzophenone 0.1% Calcium stearate 6 mil monofilament: 4O kly., 94% tensile strength retained; 70 kly., 91% tensile strength retained; 90 kly., 88% tensile strength retained When 6 mil monofilament samples were prepared as described above from unstabilized polypropylene, after 40 kly of exposure only 20% of tensile strength was retained.

Examples 37 and 38 below show how many kilolangleys of outdoor exposure polypropylene filament prepared as described above could withstand and still retain 50% of the original tenacity.

EXAMPLE 37 Polypropylene filaments containing the following additives were prepared as described above:

0.20% Nickel bis[O-n-butyl-3,5-di t butyl 4 hydroxybenzyl)phosphonate] 0.80% 2(2hydroxy-3',5-di-t-butylphenyl)-7 chlorobenzotriazole 0.07% Calcium stearate 0.20% Titanium dioxide After 55 kly.: 50% (tenacity retained) EXAMPLE 38 Polypropylene filaments containing the following additives were prepared as described above:

0.20% Nickel bis[O-n-butyl-3,5-di t butyl 4 hydroxy benzyl phosphonate] 0.80% 2-Hydroxy-4-n-octoxybenzophenone 0.07% Calcium stearate 0.20% Titanium dioxide After 90 kly.: 50% (tenacity retained) EXAMPLE 39 Polypropylene is stabilized with the following additives:

0.25% Nickel bis[(O-n-butyl-3,5-di-t-butyl-4-hydroxybenzyl)phosphonate 0.25 Dioctadecyl 3,S-di-t-butyl-4-hydroxybenzylphosphonate 0.50% 2(2'-Hydroxy-3,5-di-t-butylphenyl)-7-chlorobenzotriazole "EXAMPL AQ Polypropylene is stabilizedwith the following additives: 0.25% Nickel bis[(-O n-butyl-3,s-di-t-butyl-4 hydroxybenzynphosphonate L 0.25% Dioctadecyl 3,5-di-t-butyl-4-hydroxybenzyl- .ph p a e, v, ".25 2 2-Hydroxy-3 ',5 '-di-t-b'utylphenyl') 7-c hlorobenzotr iazole 0.25 2,4-Di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate What is claimed is: Y 1. A stabilizing composition consisting essentially of (a) organophosphoro-metal compound selected from (1) metal-organophosphonate having the formula m x[ p wherein M comprises a metal having from 1 to 4;

x has a value of from 1 to 2;

G is an anion having an available valence of from 1 to 3; and

E is of the formula:

an available valence of (lower) alkyl 2z) and wherein z has a value of from 0 to 6, y has a value of from 1 to 4, n has a value of from 0 to 1, m has a value of from 1 to 2, and p has a value of from 0 to 3,

n, m, p and at being so selected as to satisfy the expression wherein r is the valence of anion G and has a value of from 1 to 3, and v is an available valence of M, or (2) metal-organophosphinate having the formula (lower)alkyl wherein M is a metal or metal complex cation, this cation having an available valence of from 1 to 4;

g has a value of from 0 to 6;

g has a value of from 1 to 4;

(b) a phenolic antioxidant is selected from:

( Q( z)w wherein Q is A is CR(CO0R):'

50 o R :)'-Q

R is hydrogen or lower alkyl R is lower alkyl R" is alkyl group having from 6-24 carbon atoms w is an integer from 1 to 4 gem-'92 wherein T is hydrogen or Q as defined above;

(b8) CH3 (211,13

I on; 011,133

wherein B B and B are hydrogen, methyl or Q, provided that when B and B are Q then B is hydrogen and when B is Q then B and B are hydrogen Z is NHQ, SD or OQ D is alkyl group having from 6l2 carbon atoms or -(C H )--S--R7' N N Q o I wherein p is an integer from 2 to 4 and R is a tetravalent radical selected from aliphatic hydrocarbons having from 1 to 30 carbon atoms, aliphatic monoand dithioethers having from 1 to 30 carbon atoms, aliphatic monoand diethers having from 1 to 30 carbon atoms (c) an ultraviolet light absorber selected from (1) a benzophenone having the formula K is alkyl, aroyl or hydroxy, said alkyl groups in J, K,

J and K having up to 18 carbon atoms, and

wherein (2) a benzotriazole having the formula wherein L is hydrogen, alkyl, hydroxy or alkoxy group,

T is hydrogen, alkyl or alkoxy group,

L is hydrogen, alkyl or halogen group and T is hydrogen or alkyl group, said alkyl groups in L, T,

L and T having up to 18 carbon atoms;

((1) an organosulfur synergist selected from dilaurylthiodipropionate and distearylthiodipropionate; (e) a benzoate co-light stabilizer having the formula wherein (lower) alkyl wherein M, z, y, n, m and x have the values defined above;

(lower) alkyl wherein M, y', n, m and x have the values defined above; and

3. A stabilizing composition according to Claim 2 wherein M is nickel.

4. A stabilizing composition according to Claim 1 comprising (a) said metal-organophosphonate is nickel bis[O-n-butyl- 3 ,5 -di-t-butyl-4-hydroxybenzyl phosphonate] (b) said phenolic antioxidant is di-n-octadecyl-a(3-tbutyl-4-hydroxy-5-rnethylbenzyl)malonate (c) said ultraviolet light absorber is a benzotriazole or benzophenone UV absorber ((1) said secondary antioxidant is distearylthiodipropionate or dilaurylthiodipropionate.

5. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant (b) is octadecyl p-(3,5- di-t-butyl-4-hydroxyphenyl)propionate.

6. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant (b) is 2,2'-methylenebis 6-t-butyl-4-methylphenol) 7. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant is 4,4'-thiobis-(2-t-butyl- S-methylphenol) 8. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant (b) is 1,l,3-tris(3-tbutyl-4-hydroxy-fi-methylphenyl)butane.

9. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant (b) is 2,4-bis-(n-octylthio) 6 (3,5 di-t-butyl 4 hydroxyaniline) 1,3,5- triazine.

10. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant (b) is 2,4-bis(3,5-dit-butyl-4'hydroxyphenoxy) -6- n-octylthio -1,3 ,5 -triazine.

11. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant is 2,4-bis-(4-hydroxy-3, 5 di-t-butylphenoxy) 6 (n-octylthioethylthio) 1,3,5- triazine.

12. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant (b) is tetra-[3-(3',5', di-t-butyl 4 hydroxyphenyl)propionyloxyrnethyl] methane.

13. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant (b) is 1,1,1-tris-[3-(3, 5 di-t-butyl 4 hydroxyphenyl)propionyloxymethyl] propane.

14. A stabilizing composition according to Claim 4 wherein said phenolic antioxidant (b) is dioctadecyl 3,5- di-t-butyl-4-hydroxybenzylphosphonate.

15. A stabilizing composition consisting essentially of (a) 0.01 to 1% by weight of a substrate of nickel bis- [(O-ethyl 3,5 di-t-butyl-4-hydroxybenzyl) phosphonate] (b) 0.01 to 1% by weight of a substrate of dioctadecyl 3,S-di-t-butyl-4-hydroxybenzylphosphonate (c) 0.01 to 1% by weight of a substrate of n-octy1-3,5-

di-t-butyl-4-hydroxybenzoate (d) 0.01 to 1% by Weight of a substrate of 2(2-hydroxy-3 ,5 '-di-t-butylphenol) 5 -chlorobenzotriazole.

References Cited UNITED STATES PATENTS 3,310,575 3/1967 Spivack 252-400 A 3,474,147 10/ 1969 Lehikolnen 252-400 A 3,112,272 11/1963 Echols 252-400 A 3,558,747 1/ 1971 Meltsner 252-400 A 3,565,855 2/1971 Meltsner 260-4595 D 3,539,531 11/1970 Drake et a1. 252-400 A 3,297,631 1/1967 Bown et al 260-4595 D 3,335,109 8/1967 Pines 260-4595 D 3,280,070 10/ 1966 DiBattista 260-4595 D 3,145,176 8/1964- Knapp et al 257-400 A 3,244,650 4/1966 Hecker et a1 252-400 A LELAND A. SEBASTIAN, Primary Examiner I. GLUCK, Assistant Examiner US. Cl. X.R.

252-182; 260-4575 N, 45.75 R, 45.95 D 

